CN116825988A - Liquid lithium battery negative electrode coating material and preparation method thereof - Google Patents
Liquid lithium battery negative electrode coating material and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 107
- 239000011248 coating agent Substances 0.000 title claims abstract description 106
- 239000000463 material Substances 0.000 title claims abstract description 92
- 239000007788 liquid Substances 0.000 title claims abstract description 79
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000010439 graphite Substances 0.000 claims abstract description 49
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 49
- 238000002156 mixing Methods 0.000 claims abstract description 31
- 239000010405 anode material Substances 0.000 claims abstract description 20
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005977 Ethylene Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 238000004939 coking Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 46
- 239000002245 particle Substances 0.000 claims description 38
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- 238000004821 distillation Methods 0.000 claims description 15
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- 238000001704 evaporation Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000005484 gravity Effects 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 abstract description 18
- 239000011247 coating layer Substances 0.000 abstract description 8
- 239000011258 core-shell material Substances 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- -1 monocyclic aromatic hydrocarbons Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The application discloses a liquid lithium battery negative electrode coating material and a preparation method thereof, and belongs to the technical field of lithium battery negative electrode materials. The application takes ethylene tar as a raw material, and the liquid lithium battery cathode coating material is produced through the processes of filtering, distilling, polymerizing and blending in sequence. The liquid lithium battery negative electrode coating material provided by the application is used for coating the lithium battery graphite negative electrode material, and can be fully wetted and bonded with the graphite negative electrode material; the 'core-shell' structure formed by adopting the liquid coating material to treat the graphite anode material comprises an inner core and a coating layer coated on the surface of the inner core. The coating layer is firm and stable and has the characteristic of uniformity. The liquid lithium battery negative electrode coating material is in a liquid state at normal temperature and has good fluidity; the coking value is higher; easy to store and convenient to transport and use.
Description
Technical Field
The application belongs to the technical field of lithium battery negative electrode materials, and relates to a liquid lithium battery negative electrode coating material and a preparation method thereof.
Background
In the world of energy crisis today, the development of energy storage technology for lithium ion secondary batteries has become an important point of attention.
Graphite is usually selected as a negative electrode material of the lithium ion battery, and has a layered structure, so that the lithium ion battery is suitable for lithium ion deintercalation; however, graphite has poor compatibility with organic solvents, and graphite layers are easily peeled off, so that the battery has poor cycle performance, and therefore, it is necessary to modify and coat the surface of the battery to improve the electrochemical performance of the battery.
At present, the market of the lithium battery cathode coating material mainly uses solid asphalt particle products with medium and high temperature softening points (the softening points are different from 120 ℃ to 280 ℃), and reports of liquid coating materials are also presented.
The mechanical mixing is commonly called 'dry coating', the coating mode is simple, industrialization is easy to realize, but the defect is that the coating material is solid at normal temperature, asphalt powder has agglomeration and other defects in the coating process, so that the coating effect is uneven, and the electrochemical performance of the graphite cathode is affected.
Chinese patent CN115594826A discloses a low-energy-consumption synthesis method of a high-efficiency carbon cathode coating material, which comprises the steps of preheating ethylene tar raw material to 240-250 ℃, performing gas-liquid separation, then entering a polymerization reaction kettle for polymerization at 315-350 ℃ to enable polycyclic aromatic hydrocarbon components in the ethylene tar raw material to undergo high-temperature polycondensation reaction, and obtaining a product through flash evaporation after heat exchange and temperature reduction of polymerization liquid obtained by the reaction. The product of the application is low softening point coated asphalt, and the coated asphalt is in a fluid state at the use temperature during coating application, and can be fully and uniformly mixed with graphite materials. However, the product of the application is solid at normal temperature and still has certain limitation in use.
Chinese patent CN114989354a discloses a liquid lithium battery negative electrode coating material and a preparation method thereof, belonging to the liquid coating material, wherein the method comprises the steps of hydrofining heavy aromatic oil rich in anthracene and phenanthrene at 360-390 ℃ to remove sulfur, nitrogen and other impurities, thus obtaining hydrogenated heavy aromatic mixed oil; and then the heavy aromatic mixed oil is input into a polymerization kettle, mixed methylnaphthalene is added, and polymerization is carried out at 280-310 ℃. The material is liquid at normal temperature and has good fluidity. However, the process needs hydrotreating, and has the problem of higher energy consumption; and the hydrotreating process parameters are controlled more strictly.
Disclosure of Invention
In order to overcome the defects of the prior art, the application aims to provide a novel liquid lithium battery negative electrode coating material and a preparation method thereof, and the novel coating material and the preparation method thereof have feasible processes and are easy to industrialize. The novel liquid coating material is adopted to treat the graphite anode material to form a 'core-shell' structure, and the coating layer is firm and stable and shows uniformity. The novel liquid coating material is liquid at normal temperature and has good fluidity; the coking value is higher, and the graphite anode material can be fully wetted and bonded; the novel liquid negative electrode coating material is easy to store, transport and use.
The above object of the present application is achieved by the following technical solutions:
in order to achieve the above purpose, the technical scheme adopted by the application is as follows:
the preparation method of the novel liquid lithium battery negative electrode coating material comprises the following steps:
(1) Pretreatment of raw materials: filtering ethylene tar raw material by using a filter, removing impurities, purifying, and preheating raw material oil to 110-150 ℃ by using a kettle type reboiler;
(2) And (3) distilling: the ethylene tar is pretreated and then enters a reduced pressure distillation tower for distillation, the temperature of the tower bottom is 110-180 ℃, the vacuum degree is 1.0-1.5 KPa, the temperature of the tower top is 110-170 ℃, the vacuum degree is 1.0-1.5 KPa, the components at the tower top are condensed by a condenser and then flow into a liquid separating tank, and the oil phase in the liquid separating tank is refluxed and extracted; the reflux ratio is 50% -85%.
(3) Polymerization: the bottom material after distillation treatment is input into a polymerization reaction kettle, the kettle temperature is 270-330 ℃, the vacuum degree is 400-1000 Pa, and the reaction time is 40-80 minutes.
(4) Blending: and (3) firstly exchanging heat and cooling the obtained polymerization solution in the step (3) to 120-160 ℃, then inputting the polymerization solution into a blending kettle, adding mixed methylnaphthalene, continuously stirring, preserving heat for 2-3 hours, and cooling to normal temperature to obtain the novel liquid coating material.
Further, in the step (1), the specific gravity of the ethylene tar raw material at 20 ℃ is between 0.900 and 1.200/cm 3 The total sulfur content is less than 1000ppm, the initial boiling point is more than or equal to 160 ℃, the open flash point is more than or equal to 52 ℃, and the coking value is between 6.00 and 12.00 percent.
In the step (4), the mass ratio of the polymer solution to the mixed methylnaphthalene is 3:1-10:1.
Further, the mixed methylnaphthalene is industrial methylnaphthalene with the sum of the mass fractions of alpha-methylnaphthalene and beta-methylnaphthalene not lower than 60%, and the mass fraction of naphthalene content is not higher than 15.0%; the mass fraction of the water content is not higher than 1.0%.
The liquid lithium battery negative electrode coating material prepared by the preparation method has the following performance indexes: the coking value is 15-25 wt%; kinematic viscosity at 40 ℃ of 100-300 mm 2 S; the flash point of the closed mouth is more than or equal to 70 ℃; the sulfur content is less than or equal to 1100ppm.
The application of the liquid lithium battery negative electrode coating material prepared by the preparation method on the coated lithium battery negative electrode is as follows:
the liquid coating material is adopted to carry out coating treatment on graphite anode particles, and the method specifically comprises the following steps:
(a) Mixing graphite particles with the particle size of 14-25 mu m and the coating material in a mixer, wherein the temperature is controlled at 80-140 ℃ in the mixing process, and the weight ratio of the novel liquid coating material to the graphite particles is 1:6-1:12;
(b) Heating the mixer to 160-250 ℃, simultaneously maintaining negative pressure to enable the novel liquid coating material to fully coat graphite particles, and continuously evaporating to dryness;
(c) And (3) carbonizing and graphitizing the product obtained after the step (b) is evaporated to dryness to obtain the graphite anode material modified by the novel liquid coating material.
The application takes ethylene tar as a raw material, and the liquid lithium battery cathode coating material is produced through the processes of filtering, distilling, polymerizing and blending in sequence. The liquid lithium battery negative electrode coating material provided by the application is used for coating the lithium battery graphite negative electrode material, and can be fully wetted and bonded with the graphite negative electrode material; the 'core-shell' structure formed by adopting the liquid coating material to treat the graphite anode material comprises an inner core and a coating layer coated on the surface of the inner core. The coating layer is firm and stable and has the characteristic of uniformity. The liquid lithium battery negative electrode coating material is in a liquid state at normal temperature and has good fluidity; the coking value is higher; easy to store and convenient to transport and use.
Compared with the prior art, the application has the beneficial effects that:
1. ethylene tar is used as a raw material, wherein the coking value of the coating material is effectively improved through distillation and polymerization, and the coating time is further shortened.
2. The application adopts distillation-polymerization-blending technology, is convenient for production control and is convenient for the production of liquid coating materials.
3. The novel coating material is in a liquid state at normal temperature and has relatively good fluidity; the high coking value is achieved, and the high-temperature-resistant graphite can be fully wetted and bonded with a graphite negative electrode material; the core-shell structure is stable and the coating layer is uniform. Easy to store and convenient to transport and use.
The application aims to provide a novel liquid lithium battery negative electrode coating material and a preparation method thereof, wherein ethylene tar is used as a raw material, and a specific preparation method is limited, so that the novel liquid lithium battery negative electrode coating material is easy to control and convenient to produce; the prepared liquid coating material can improve the uniformity of coating and simultaneously improve the electrochemical performance of the graphite anode material.
Drawings
Fig. 1 is a schematic structural view of a negative electrode material according to an embodiment of the present application;
fig. 2 is a schematic flow chart of the process for preparing a liquid clad material according to the present application.
In the figure: 1-a negative electrode material; 2-coating layer; 3-kernel.
Detailed Description
The present application is described in detail below by way of specific examples, but the scope of the present application is not limited thereto. Unless otherwise specified, the experimental methods used in the present application are all conventional methods, and all experimental equipment, materials, reagents, etc. used can be obtained from commercial sources.
Example 1
Example 1:
in this example, a new liquid negative electrode coating material was prepared by pretreatment, distillation, polymerization, and blending of raw ethylene tar, as shown in fig. 1.
Ethylene tar, i.e. ethylene cracking tar, is a brown black liquid with a density of 1.0893g/cm at 20deg.C 3 The total sulfur content is 996ppm, the initial boiling point is more than or equal to 160 ℃, the open flash point is more than or equal to 52 ℃ and the coking value is 10.04%. The distillation ranges are shown in Table 1 below and the compositions are shown in Table 2.
Table 1 distillation ranges: (v/v) (in the table, the percentages are all by volume)
| ％ | ℃ | ％ | ℃ | ％ | ℃ |
| IBP | 59℃ | 40％ | 327℃ | 90％ | 622℃ |
| 5％ | 138℃ | 50％ | 422℃ | 95％ | 667℃ |
| 10％ | 217℃ | 60％ | 493℃ | ||
| 20％ | 253℃ | 70％ | 568℃ | ||
| 30％ | 275℃ | 80％ | 594℃ |
TABLE 2 compositional analysis
| Composition (Wt)/% | Numerical value |
| Total monocyclic aromatic hydrocarbons | 15.2 |
| Total bicyclic aromatic hydrocarbons | 30.2 |
| Total tricyclic aromatic hydrocarbons | 14.3 |
| Total tetracyclic aromatic hydrocarbons | 12.1 |
| Total pentacyclic aromatic hydrocarbons | 5.1 |
| Total hexacyclic and other aromatic hydrocarbons | 17.9 |
| Colloid | 5.2 |
2. Pretreatment: filtering ethylene tar raw material by using a filter, removing impurities, purifying, and preheating raw material oil to 140 ℃ by using a kettle type reboiler;
3. and (3) distilling: and (3) inputting the pretreated ethylene tar into a reduced pressure distillation tower for distillation.
In the distillation process, the temperature of the tower bottom is 140 ℃, the vacuum degree is 1.3KPa, the temperature of the tower top is 130 ℃, the vacuum degree is 1.3KPa, the components at the tower top are condensed by a condenser and then flow into a liquid separating tank, and the oil phase in the liquid separating tank is refluxed and extracted. The tower bottom enters a polymerization kettle for polymerization. The results of the bottoms detection are shown in Table 3.
TABLE 3 analysis of distillation bottoms detection
| Softening point of | Coking value (wt%) | Quinoline insolubles | Ash (wt%) |
| 31(±1) | 11～12 | 0 | 0.001 |
4, polymerization: the bottom product after distillation treatment was fed into a polymerization reactor at 270℃and 800Pa for 60 minutes under vacuum, and the detection results of the polymerization products were shown in Table 4.
Ethylene tar raw material mainly comprises polycyclic aromatic hydrocarbon, wherein the polycyclic aromatic hydrocarbon mainly generates cracking and condensation reaction, on one hand, C-H bond breakage generates dehydrogenation, and aromatic hydrocarbon side chain C-C bond breakage generates cracking; on the other hand, aromatic hydrocarbon molecules are condensed, and the original 3-5 ring aromatic hydrocarbon is condensed into ring aromatic hydrocarbon with more carbon numbers.
The reaction is carried out in a polymerization kettle,
(5) Blending: and (3) firstly exchanging heat and cooling the obtained polymerization solution in the step (3) to 140 ℃, then inputting the polymerization solution into a blending kettle, adding mixed methylnaphthalene, continuously stirring, preserving heat for 2.5 hours, and cooling to normal temperature to obtain the novel liquid coating material.
Mixed methylnaphthalene: the sum of the mass fractions of the alpha-methylnaphthalene and the beta-methylnaphthalene is 61 percent, and the mass fraction of the naphthalene content is 14 percent.
And (3) carrying out heat exchange and cooling on a polymerization product with the polymerization temperature of 270 ℃, cooling to 140 ℃, adding mixed methylnaphthalene, wherein the sulfur content of the mixed methylnaphthalene is 853ppm, the ratio of the polymerization product to the mixed methylnaphthalene is 4.6:1, and the coking value of the novel coating material prepared after blending is shown in Table 5.
Example 2:
step 4, the kettle temperature in the polymerization is 280 ℃, and the mixture is mixed with methylnaphthalene: the sum of the mass fractions of the alpha-methylnaphthalene and the beta-methylnaphthalene is 62 percent, and the mass fraction of the naphthalene content is 13 percent.
Otherwise, the same as in example 1 was conducted. The polymerization product detection results are shown in Table 4. The coking values of the novel coating materials obtained after blending are shown in Table 5.
Example 3:
step 4, the kettle temperature in the polymerization is 290 ℃, and the mixture is mixed with methylnaphthalene: the sum of the mass fractions of the alpha-methylnaphthalene and the beta-methylnaphthalene is 63 percent, and the mass fraction of the naphthalene content is 12 percent.
Otherwise, the same as in example 1 was conducted. The polymerization product detection results are shown in Table 4. The coking values of the novel coating materials obtained after blending are shown in Table 5.
Example 4:
step 4, the kettle temperature in the polymerization is 300 ℃, and the mixture is mixed with methylnaphthalene: the sum of the mass fractions of the alpha-methylnaphthalene and the beta-methylnaphthalene is 64 percent, and the mass fraction of the naphthalene content is 11 percent.
Otherwise, the same as in example 1 was conducted. The polymerization product detection results are shown in Table 4. The coking values of the novel coating materials obtained after blending are shown in Table 5.
TABLE 4 polymerization product detection analysis
| Examples | Softening point/. Degree.C | Coking value/% | Quinoline insoluble/% | Ash/% |
| Example 1 | 36(±1) | 21～22 | 0 | 0.001 |
| Example 2 | 39(±1) | 23～24 | 0 | 0.001 |
| Example 3 | 43(±1) | 25～26 | 0 | 0.001 |
| Example 4 | 47(±1) | 28～29 | 0 | 0.001 |
Table 5 novel liquid coating material detection data
The coating materials obtained by blending example 1, example 2, example 3 and example 4 were subjected to performance test, and the test data are shown in table 6.
TABLE 6 novel liquid coating Material technical index data
| Examples | Kinematic viscosity at 40 ℃ per mm 2 /s | Closed flash point/°c | Sulfur content/ppm |
| Example 1 | 221.3 | 84 | 784 |
| Example 2 | 240.9 | 88 | 790 |
| Example 3 | 256.6 | 89 | 792 |
| Example 4 | 275.4 | 91 | 800 |
Application example 1:
the coating material prepared in example 1 was used for coating a lithium battery anode material, and comprises the following steps:
(a) Mixing graphite particles with the particle size of 14-20 mu m and the coating material in a mixer, wherein the temperature is controlled at 120 ℃ in the mixing process, and the weight ratio of the novel liquid coating material to the graphite particles is 1:8;
(b) Heating the mixer to 200 ℃, keeping negative pressure at the same time, so that the novel liquid coating material fully coats graphite particles, and continuously evaporating to dryness;
(c) And (3) carbonizing and graphitizing the product obtained after the step (b) is evaporated to dryness to obtain the novel liquid coating material modified graphite anode material. The detection data are shown in Table 7 by measuring the average particle diameter and specific surface area of the negative electrode material.
Application example 2
The coating material prepared in example 2 was used for coating a lithium battery anode material, and comprises the following steps:
(a) Mixing graphite particles with the particle size of 14-20 mu m and the coating material in a mixer, wherein the temperature is controlled at 120 ℃ in the mixing process, and the weight ratio of the novel liquid coating material to the graphite particles is 1:8;
(b) Heating the mixer to 200 ℃, keeping negative pressure at the same time, so that the novel liquid coating material fully coats graphite particles, and continuously evaporating to dryness;
(c) And (3) carbonizing and graphitizing the product obtained after the step (b) is evaporated to dryness to obtain the novel liquid coating material modified graphite anode material. The detection data are shown in Table 7 by measuring the average particle diameter and specific surface area of the negative electrode material.
Application example 3
The coating material prepared in example 3 was used for coating a lithium battery anode material, and comprises the following steps:
(a) Mixing graphite particles with the particle size of 14-20 mu m and the coating material in a mixer, wherein the temperature is controlled at 120 ℃ in the mixing process, and the weight ratio of the novel liquid coating material to the graphite particles is 1:8;
(b) Heating the mixer to 200 ℃, keeping negative pressure at the same time, so that the novel liquid coating material fully coats graphite particles, and continuously evaporating to dryness;
(c) And (3) carbonizing and graphitizing the product obtained after the step (b) is evaporated to dryness to obtain the novel liquid coating material modified graphite anode material. The detection data are shown in Table 7 by measuring the average particle diameter and specific surface area of the negative electrode material.
Application example 4
The coating material prepared in example 4 was used for coating a lithium battery anode material, and comprises the following steps:
(a) Mixing graphite particles with the particle size of 14-20 mu m and the coating material in a mixer, wherein the temperature is controlled at 120 ℃ in the mixing process, and the weight ratio of the novel liquid coating material to the graphite particles is 1:8;
(b) Heating the mixer to 200 ℃, keeping negative pressure at the same time, so that the novel liquid coating material fully coats graphite particles, and continuously evaporating to dryness;
(c) And (3) carbonizing and graphitizing the product obtained after the step (b) is evaporated to dryness to obtain the novel liquid coating material modified graphite anode material. The detection data are shown in Table 7 by measuring the average particle diameter and specific surface area of the negative electrode material.
Comparative example 1 was applied.
Taking graphite particles with the diameter of 14-20 mu m; the solid phase coated asphalt powder and the taken graphite particles with the diameter of 14-20 mu m are fully mixed according to the solid phase mixing method according to the proportion of 1:14, are molded into blocks by a press machine, are carbonized and graphitized, are crushed and sieved to obtain the graphite anode material with the diameter of 14-20 mu m coated by the solid phase asphalt, and are used as a control. The test data are shown in Table 7.
Comparative example 2 was used
The coating material prepared by Chinese patent CN114989354A is used for coating the negative electrode material of the lithium battery, and comprises the following steps:
mixing graphite particles with the particle size of 14-20 mu m with a coating material prepared by Chinese patent CN114989354A in a mixer, wherein the temperature is controlled at 120 ℃ in the mixing process, and the weight ratio of the liquid coating material prepared by Chinese patent CN114989354A to the graphite particles is 1:8; heating the mixer to 200deg.C while maintaining negative pressure to make the liquid coating material prepared by Chinese patent CN114989354A fully coat graphite particles, and continuously evaporating to dryness; and carbonizing and graphitizing the product obtained after the evaporation to dryness to obtain the graphite anode material modified by the coating material, which is prepared by Chinese patent CN 114989354A. The detection data are shown in Table 7 by measuring the average particle diameter and specific surface area of the negative electrode material.
The test data are shown in Table 7.
Table 7 modified graphite negative electrode Material detection data
As can be seen from the test results in table 7, the specific surface area of the liquid phase coated anode material is significantly reduced compared with that of the solid phase coated anode material, which indicates that the coating of the liquid phase coated material is more uniform.
The graphite anode materials obtained in application examples 1 to 4 and comparative examples 1 to 2 prepared in examples 1 to 4 were tested for the first discharge capacity and the first charge-discharge efficiency, and the test data are shown in table 8.
Table 8 electrochemical performance test data
| Sequence number | First discharge capacity mAh/g | The first charge and discharge efficiency is% |
| Application example 1 | 362.4 | 94.1 |
| Application example 2 | 361.2 | 95.6 |
| Application example 3 | 363.5 | 96.2 |
| Application example 4 | 361.0 | 95.3 |
| Comparative example 1 was used | 353.0 | 91.0 |
| Comparative example 2 was used | 358.6 | 92.8 |
From the test data in table 8, it can be seen that the liquid negative electrode coating material prepared by the application coats the graphite negative electrode of the lithium battery, the electric conductivity is good, the cohesiveness is stronger, the first effect of the coated graphite negative electrode material is obviously improved, the electrochemical performance of the lithium battery can be effectively improved, and the application example 3 prepared in example 3 has the best effect. In comparative example 2, the coating layer formed is too thick, increasing the resistance to ingress and egress of lithium ions, resulting in a portion of lithium ions failing to escape from the graphite negative electrode, resulting in a decrease in capacity. As shown in table 8, the liquid coating material prepared in chinese patent CN114989354a was better than the dry coating for coating graphite negative electrode, but not as good as the present patent.
The comparison of the preferred embodiment 3 of the present application with the prior art is shown in the following table:
the above-described embodiments are only preferred embodiments of the application, and not all embodiments of the application are possible. Any obvious modifications thereof, which would be apparent to those skilled in the art without departing from the principles and spirit of the present application, should be considered to be included within the scope of the appended claims.
Claims (6)
1. The preparation method of the liquid lithium battery negative electrode coating material is characterized by comprising the following steps of:
(1) Pretreatment of raw materials: filtering ethylene tar raw material by using a filter, removing impurities, purifying, and preheating raw material oil to 110-150 ℃ by using a kettle type reboiler;
(2) And (3) distilling: the ethylene tar is pretreated and then enters a reduced pressure distillation tower for distillation, the temperature of the tower bottom is 110-180 ℃, the vacuum degree is 1.0-1.5 KPa, the temperature of the tower top is 110-170 ℃, the vacuum degree is 1.0-1.5 KPa, the components at the tower top are condensed by a condenser and then flow into a liquid separating tank, and the oil phase in the liquid separating tank is refluxed and extracted.
(3) Polymerization: the bottom material after distillation treatment is input into a polymerization reaction kettle, the kettle temperature is 270-330 ℃, the vacuum degree is 400-1000 Pa, and the reaction time is 40-80 minutes;
(4) Blending: and (3) firstly exchanging heat and cooling the polymerization liquid obtained in the step (3) to 120-160 ℃, then inputting the polymerization liquid into a blending kettle, adding mixed methylnaphthalene, continuously stirring, preserving heat for 2-3 hours, and cooling to normal temperature to obtain the liquid coating material.
2. The method for preparing a negative electrode coating material for a liquid lithium battery according to claim 1, wherein in the step (1), the specific gravity of the ethylene tar raw material at 20 ℃ is 0.900-1.200/cm 3 The total sulfur content is less than 1000ppm, the initial boiling point is more than or equal to 160 ℃, the open flash point is more than or equal to 52 ℃, and the coking value is between 6.00 and 12.00 percent.
3. The method for preparing a liquid lithium battery anode coating material according to claim 2, wherein in the step (4), the mass ratio of the polymer solution to the mixed methylnaphthalene is 3:1-10:1.
4. The method for preparing a liquid lithium battery negative electrode coating material according to claim 3, wherein the mixed methylnaphthalene is industrial methylnaphthalene with the sum of the mass fractions of alpha-methylnaphthalene and beta-methylnaphthalene not lower than 60%, and the mass fraction of naphthalene content is not higher than 15.0%; the mass fraction of the water content is not higher than 1.0%.
5. Use of a liquid lithium battery negative electrode coating material prepared by the preparation method of any one of claims 1-4 for coating a lithium battery negative electrode.
6. The application of the liquid lithium battery negative electrode coating material to the coating lithium battery negative electrode as claimed in claim 5, wherein the coating treatment of the graphite negative electrode particles by the liquid coating material comprises the following steps:
(a) Mixing graphite particles with the particle size of 14-25 mu m and the coating material in a mixer, wherein the temperature is controlled at 80-140 ℃ in the mixing process, and the weight ratio of the liquid coating material to the graphite particles is 1:6-1:12;
(b) Heating the mixer to 160-250 ℃, simultaneously maintaining negative pressure to enable the liquid coating material to fully coat the graphite particles, and continuously evaporating to dryness;
(c) And (3) carbonizing and graphitizing the product obtained after the step (b) is evaporated to dryness to obtain the graphite anode material modified by the liquid coating material.
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|---|---|---|---|
| CN202310750682.7A CN116825988A (en) | 2023-06-25 | 2023-06-25 | Liquid lithium battery negative electrode coating material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310750682.7A CN116825988A (en) | 2023-06-25 | 2023-06-25 | Liquid lithium battery negative electrode coating material and preparation method thereof |
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| CN202310750682.7A Pending CN116825988A (en) | 2023-06-25 | 2023-06-25 | Liquid lithium battery negative electrode coating material and preparation method thereof |
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